Novel Catalysts for the Environmentally Friendly Synthesis of Methyl Methacrylate
Novel Catalysts for the Environmentally Friendly Synthesis of Methyl Methacrylate
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DOI：
10.1021/ie970139r
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发表时间：
1997-11
影响因子：
4.2
通讯作者：
J. Spivey;M. Gogate;J. Zoeller;R. Colberg
中科院分区：
文献类型：
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作者：
J. Spivey;M. Gogate;J. Zoeller;R. Colberg
开发由煤衍生合成气合成甲基丙烯酸甲酯（MMA）的工艺可以减轻与当前商业MMA技术（丙酮氰醇（ACH）工艺）相关的环境危害。基于合成气的三步工艺包括合成丙酸、其与甲醛的缩合以及所得甲基丙烯酸（MAA）的酯化形成MMA。前两个步骤，丙酸合成和缩合，在这里讨论。乙烯一步加氢羰基化制丙酸的低温低压工艺是使用均相碘促进的Mo（CO）6催化剂在低于其他催化剂的压力（30 - 70 atm）和温度（150 - 200 °C）下进行的。机理研究表明，催化是由一个限速CO解离Mo（CO）6。这种解离似乎伴随着I原子从EtI到配位不饱和……的内部电子转移过程。
The development of a process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas can alleviate the environmental hazards associated with the current commercial MMA technology, the acetone cyanohydrin (ACH) process. A three-step syngas-based process consisted of synthesis of a propionic acid, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) to form MMA. The first two steps, propionic acid synthesis and condensation, are discussed here. The low-temperature, low-pressure process for single-step hydrocarbonylation of ethylene to propionic acid is carried out using a homogeneous iodine-promoted Mo (CO)6 catalyst at pressures (30−70 atm) and temperatures (150−200 °C) lower than those reported for other catalysts. Mechanistic investigations suggest that catalysis is initiated by a rate-limiting CO dissociation from Mo(CO)6. This dissociation appears to be followed by an inner electron-transfer process of an I atom from EtI to the coordinately unsatura...